The opportunities for the marketing of agroecological products in China have grown in recent years due to the increasing awareness of the food safety issues, the increase of middle to high income groups, and the extension and improvement of the rural internet facilities. The agroecological transition provides an important opportunity for mountainous agriculture, which does not have the advantage of large scale production. However, the reality in the mountainous rural areas are very severe, including environmental degradation, deterioration of soil quality, demographic changes, and farmers’ limited access to capital and modern technology. These kinds of challenges are explored through the representative case study in Sanliwan village of Shanxi province. By comparing Sanliwan village to other cases in China using an agroecological framework, we find that organized farmers have a greater capacity to make the agroecological transition, such as the ability to learn and apply the new agricultural technologies, the resistance to market conditions, the ability to seek help from different sources, and the increase to the value of agricultural products. Therefore, the transition to agroecology is not simply a technical challenge, but also involves the politics, economy, education, organization and cultural backgrounds of the people involved. An agroecological transition for the mountainous regions of China will require a holistic perspective that considers multiple scales.